Catechol Containing Polyhydroxyurethanes as High Performance

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Catechol Containing Polyhydroxyurethanes as High Performance Coatings and Adhesives Satyannarayana Panchireddy, Bruno Grignard, Jean-Michel Thomassin, Christine Jerome, and Christophe Detrembleur ACS Sustainable Chem. Eng., Just Accepted Manuscript • DOI: 10.1021/ acssuschemeng.8b03429 • Publication Date (Web): 03 Oct 2018 Downloaded from http://pubs.acs.org on October 3, 2018

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ACS Sustainable Chemistry & Engineering

Catechol Containing Polyhydroxyurethanes as High Performance Coatings and Adhesives Satyannarayana Panchireddy, Bruno Grignard, Jean-Michel Thomassin, Christine Jerome, Christophe Detrembleur* Center for Education and Research on Macromolecules (CERM), CESAM Research Unit, University of Liège, allée du 6 août, Building B6A, Agora Square, 4000 Liège, Belgium

KEYWORDS Polyhydroxyurethane, non-isocyanate polyurethane, adhesives, coatings, carbon dioxide chemistry, solvent-free synthesis

AUTHOR INFORMATION To whom correspondence should be addressed: Tel: +3243663465 *E-mail: [email protected] (Christophe Detrembleur)

ACS Paragon Plus Environment

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ABSTRACT

Green routes for the synthesis of high performant isocyanate-free polyurethane coatings and adhesives are intensively searched for. In this paper, we report a solvent- and isocyanate-free formulation for novel poly(hydroxyurethane) glues bearing strongly adherent catechol groups. These adhesives are prepared by the polyaddition of a CO2-sourced tricyclic carbonate, hexamethylene diamine and a catecholamine (dopamine). The role of the catechol functions on the PHU curing and on the final PHU properties are investigated. Although the dopamine slows down the curing of the formulation, this catecholamine added at only 3.9 mol% impressively improves the mechanical and adhesion performances of PHU. The lap shear adhesion of our product surpasses those of PHU that do not contain the catechols. We also demonstrate that the catechol-bearing PHU glues are competing with the adhesion performances of commercial PU glues, at least when a thermal curing is implemented to overcome the low reactivity of cyclic carbonate with amines. The use of renewable feedstocks, the solvent-free process, the atom economy polyaddition reaction, and the absence of any toxic reagent benefit to the sustainability of the final product.


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INTRODUCTION Due to their tunable bonding strength, design flexibility, durability and cost effectiveness, polymer-based adhesives are broadly diversified in our daily life with applications ranging from post-it notes to aerospace industry.1–8 A large palette of adhesives are found on the market place such as those made of cyanoacrylate (Super Glue), epoxy resins, and polyurethane to cite only a few. The main common drawback of many commercial adhesives is that they are produced from some toxic compounds. The production of high performance adhesives by greener routes and eventually from renewable resources is gaining increasing interest. Polyurethane (PU)-based adhesives are largely used for bonding metal substrates due to their high adhesion strength.9–14 However, the classical method for their production uses isocyanates that are toxic and so have associated health concerns.15–18 PUs adhesives prepared by greener alternatives are thus searched for, but their adhesive performances have to compete with those of conventional PUs. The polyaddition of di(poly)cyclic carbonates with di(poly)amines is an attractive strategy for producing poly(hydroxyurethane)s (PHUs), a green variant for conventional PUs.19–30 The presence of an hydroxyl group in the ß-position of the urethane contributes to the improvement of the adhesion with various substrates, the chemical resistance and mechanical properties of the polymer due to multiple hydrogen bondings31–33 Only few recent reports are describing the potential of PHUs as adhesives. PU/PHU hybrid adhesives produced from cyclic carbonates and functional α,ω-telechelic isocyanate-based PU prepolymers with polyamines achieved good adhesion onto some polymers (polyimide, poly(vinyl chloride)) but also on aluminum.34 However, these adhesives are still using some conventional PUs in their formulations. Caillol et al.35 recently reported the preparation of all PHU glues with high adhesion strength (≈15 MPa) on wood and glass but their adhesion on painted aluminum was


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moderate (≈3 MPa). Hybrid poly(dimethyl siloxane) (PDMS)-hydroxyurethanes formulations achieved 7 MPa on glass and 0.9-1.7 MPa on metal (stainless steel, titanium and aluminum).36,37 Our group recently reported on the solvent-free preparation of PHU thermosets reinforced by ZnO nanoparticles that presented a high shear adhesion strength (up to 16.3 MPa) on aluminum.32 We highlighted that the reinforcement of PHU with ZnO particles strongly improved the adhesion of PHU by 270%, leading to PHU adhesives with competitive adhesion strength compared to commercial PU-adhesives. Cyclocarbonated vegetable oils combined to amines and reinforced with ZnO particles provided also more sustainable adhesives.33 Although high adhesion performances were achieved for these PHUs, the lap shear strength of the commercial PU glues were still higher. In order to improve adhesion in wet environment, researchers were recently inspired by marine mussels.38–40 The excellent adhesion of these organisms to any substrates was attributed to the presence of large quantity of 3,4-dihydroxyphenylalanine in their surface proteins.41–47 The catechol of 3,4-dihydroxyphenylalanine has indeed the ability to form a large diversity of chemical interactions and to self-crosslink, helping the proteins to solidify and to bind tightly to various types of surfaces.48 Messersmith et al.49–51 demonstrated that polydopamine (PDA) served as a universal surface-modifying agent for virtually any substrates thanks to the presence of covalent and reversible coordination bonds between catechol groups and the surface.52–55 Recent studies have revealed that PDA-modified-PU can be used as catalytic supports,56,57 and that PDA modification can enhance the flame retardancy58 and mechanical properties of the PU.59–61 The dopamine-containing-PU showed adhesive strength of 5.2 MPa on iron.62 The design of mussel-inspired isocyanate-free PU adhesive materials may generate a new class of high performance materials competing with conventional PUs. To the best of our knowledge, the


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development of high performance adhesives by incorporating pendent catechol groups into the backbone of PHUs has never been reported. With the main purpose to develop sustainable high performance PHU adhesives, we describe the solvent-free preparation of PHUs thermosets bearing catechols by the addition of a catecholamine, dopamine (DOP), to the formulation of the multifunctional cyclic carbonate and the diamine (Scheme 1). The addition of DOP is expected to improve both the cohesive strength of the adhesive and the interaction with the substrates. In this study, we systematically study the influence of the addition of DOP on the rate of crosslinking, the thermomechanical and the adhesion properties of the crosslinked PHUs. The best adhesive formulation is then investigated on a large diversity of substrates (aluminum, stainless steel, plexiglass, wood, and polyethylene), and is benchmarked to commercial PU glues and state-of-the-art PHU adhesives.

F3C

CF3 CF3 H F3C O H H O

O

HO CH3

CH3

O

NH

O

NH

HO

O

O

O

O

N I

OH

N H

OH HO

OH

O H3C

O

CH3

O

NH

O O

O

O

O

HO

O

CO2

O

OH O

O

N H

O

O OH O

OH O O

OH

O O

O O O

O

NH

O H2 N

O

NH

NH2

O

O

OH

O O O

TMPTC

O

O

O

HO H2N

OH O

OH

O

At temperature applied DOP (0-14.8 mol%)

Solvent free-

Mussel-mimetic-PHU-Thermosets

Adhesives/Coatings

Scheme 1. Design and synthesis of mussel-mimetic-polyhydroxyurethane solvent-free adhesives.


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EXPERIMENTAL SECTION Materials and methods. Trimethylolpropane triglycidyl ether (TMPTE), tetrabutylammonium iodide (TBAI, purity >99%), hexamethyl diamine (HMDA), dopamine hydrochloride (DOP), pyrocatechol, methanol was purchased from sigma Aldrich. Carbon dioxide (CO2) N45 was supplied by Air liquid. 1,3-bis (2-hydroxyhexafluroisopropyl)-benzene was purchased from Fluorochem. All chemicals were used as received without any further purification. Al-2024-T3 (thickness of 0.8 mm) substrates were received from SONACA, Belgium. Stainless steel (316AK steel, thickness of 1 mm) and plexiglass (poly(methyl methacrylate) PMMA, thickness of 3 mm) kindly supplied by Testas (Belgium) and Plastiservice (Belgium), respectively. Wood (beech, thickness of 10 mm) substrates was purchased from Brico and plastics (high density polyethylene, HDPE, thickness of 3 mm) developed in the lab. Surface treatments. The substrates surfaces [aluminum (Al), stainless steel (SS), plexiglass (Gl), wood (W) and polyethylene (PE)] were cut into desired dimensions (50 mm × 10 mm) and surfaces were cleaned to degrease the unwanted weak boundary layers such as surface contaminants, oil, grease, oxides, etc. The scrubbing of Al-substrates was similar to our previously reported method.32,33 SS, Gl, W and PE substrates were cleaned with an acetone/isopropanol (1/1, v/v) mixture followed by washing with water. The procedure was repeated 3 times and then, the substrate was wiped with tissue paper and dried at room temperature for 2 h. Preparation of polymeric coatings and films. Prior to prepare solvent free thermoset coatings and films, the required amount of dopamine (Table 1) was dissolved in MeOH (3 mL), added to TMPTC (2.0 g, 4.6 mmol) and heated at 60 °C for 5 min. The reaction mixture was allowed to


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stir for 20 min at room temperature until an homogeneous solution was obtained, and then solvent was removed under vacuum. Subsequently, a stoichiometric amount of HMDA (compared to cyclic carbonates, see Table 1) was added into the reaction mixture that was then stirred for 1 min at 60 °C and 2 min at room temperature to obtain homogeneous mixture. Then, the viscous mixture was deposited on bare aluminum (Al-2024-T3) by using a bar-coat applicator (ASTM D823) to obtain a coating thickness in the range of 50–60 µm. All coatings were repeated 6 times for evaluating the reproducibility. The coated substrates were cured at 100 °C for 18 h in an oven. These coatings were then evaluated for crosscut adhesion test, and contact angle measurements. The freestanding films with 5 mm thickness were prepared by pouring the viscous DOP/TMPTC/HMDA mixtures into Teflon mold (3.5 × 3.5 × 0.5) cm3 for the determination of the water content (EWC), gel content (GC), contact angle and thermal properties. Additionally, dog-bone-shaped samples were made using Teflon molds for the evaluation of the mechanical properties. The samples were cured in oven at 100 °C for 18 h. Preparation of lap-shear joints. The adhesive joints were prepared to determine tensile lap shear adhesion strength of the designed thermosets. The viscous oligomeric solutions (~ 10 mg) was deposited onto the cleaned substrates with an overlapped gluing area of 100 mm2 and the second substrate was placed into contact. Then the samples were pressed gently with fingers, without formation of defects and/or squeezed out of the adhesive in the joints. The adhesively bonded joints were allowed to cure in an oven at 100 °C for 18 h. CHARACTERIZATION METHODS


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Fourier transform infrared spectra (FTIR) measurements. They were carried out on Nicolet IS5 spectrometer (Thermo Fisher Scientific) equipped with a diamond attenuated transmission reflectance (ATR) device, 32 scans were recorded for each sample over the range of 4000-500 cm–1 with a normal resolution of 4 cm-1 and spectra were analyzed with ONIUMTM software. Rheology measurements. The influence of the content of dopamine on PHU solvent-free formulations (~ 0.5 g) was determined by rheology measurements carried out on ARES from Rheometric scientific TA instrument at 100 °C for 40 min at a frequency of 1 Hz and a strain of 1% using time sweep measurements. The crosslinking density (e) of the networks was calculated from rubbery plateau region by using the formula.63,64 e = G´/3RT

(1)

Where G´ is the storage modulus of thermoset in the rubbery plateau region at 100 °C for 40 min, R is gas constant and T is the absolute temperature Thermal characterizations. Thermogravimetric analysis (TGA) of the coatings was evaluated using a Q500 from TA instruments at heating rate of 20 °C min−1 over the temperature range of 0 to 700 0C under nitrogen atmosphere. DSC (Differential scanning calorimetry) analysis was carried out on a Q1000 from TA instruments using standard aluminum pans, calibrated with indium and nitrogen as purge gas. The samples were measured at a heating rate of 10 °C min−1 over a temperature range from −80 °C to 200 °C under a flowing nitrogen atmosphere, using TA analysis software provided with the instrument. Tensile properties. The measurements were performed at room temperature using an Instron 5594 tensile machine at a speed of 10 mm min−1 with a load capacity of 10,000 N applied forces perpendicular to the adhesive materials. Young’s modulus (E), Ultimate tensile strength (σu) and


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Fracture stress (σf) were estimated by the average values of at least 6 repeated flat dog-bone shaped samples with the following dimensions, i.e., length = 3 cm, length of narrow fraction = 1 cm, width = 0.5 cm, width of narrow fraction = 0.2 cm and thickness = 0.05 cm. Swelling behaviour and gel content. Equilibrium water swelling of PHU samples was evaluated by measuring water content of free-standing films at room temperature.21 After curing process, PHU samples of 0.125 cm3 were immersed in 10 mL of milli-Q water or THF at room temperature for 96 h. The amount of water or THF was measured until the weight of the swollen samples remains constant. Equilibrium water content (EWC) was measured as function of time using equation (1). After swelling measurements, samples were dried in oven at 70 °C for 24 h. Gel content was measured using equation (2): EWC (%) =

Ws -Wi Wi

X 100

GC (%) = f X 100 W

Wi

(2)

(3)

Where Ws is the weight of swollen sample, Wi is the initial weight and Wf is the final weight of the dried sample. Crosscut adhesion tests. Crosscut adhesion tests were carried out according to ASTM D3359 standards. A cross-hatch cut pattern consisting of six vertical parallel lines and six horizontal lines separated by 3 mm was created onto series of PHU coated aluminum substrates with a sharp razor blade followed by the application of a high-pressure sensitive adhesive tape (Intertape tm 51596-ASTM D3359, Gardco). The tape is then removed by rapid pulling off at an angle of 180°. The quality of the coating was visually estimated by comparison with percentage


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(%) of area removed from the total surface. The coatings were classified as 5B: 0% of the coating removed. Water contact angle measurements. Measurements were obtained on an OCA-20 apparatus (Dataphysics Instrument GmbH) in the sessile drop configuration by depositing a 5-µL droplet of milli-Q water. Mean contact angle values were determined from at least 5 repeated measurements realized at different locations of each Al coated surfaces. Lap-shear tests. The adhesion properties of thermosets were evaluated at 298K (load or force (N) as function of displacement (mm) using an Instron 5594 equipped with a 10,000 N load cell and applied force parallel to the adhesive bond with displacement rate of 2 mm min−1 until pulling apart the bonded joints. The substrates with dimensions of 50 mm × 10 mm were used for single lap-shear measurements and gripping length on both sides of test specimens was 25 mm. The tests were performed on 5 repeated samples from each type of adhesive to determine average lap-shear adhesion strength of adhesives. The lap shear strength was calculated by the formula. τ =

(4)

Where, τ is lap shear strength (in N mm−2 or MPa), P is the maximum loading force to remove & break the adhesive (N) and A is the overlapped or gluing area of adhesive joint (100 mm2). RESULTS AND DISCUSSION Modified PHU thermosets were synthesized by reaction between a tri-functional cyclic carbonate, i.e. trimethylolpropane tris-carbonate (TMPTC), HMDA and DOP under equimolar conditions between the cyclic carbonate and the amine groups (Scheme 1). TMPTC was synthesized in kilogram scale by the solvent-free organocatalyzed coupling of carbon dioxide


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with TMPTE.65–69 A pre-mixing of TMPTC and DOP was carried out in methanol in order to obtain an homogeneous solution before removing the solvent under vacuum, followed by the addition of HMDA. The formulations were then cured at 100 °C. The conversion of cyclic carbonates into PHUs was monitored by FTIR spectroscopy (Fig.1) with the disappearance of cyclic carbonate band at 1782 cm-1 and the appearance of characteristic bands of neat and mussel-mimetic PHUs at νmax (cm-1) 3316 (O−H, N−H), 1697 (C=O), 1539 (δ(N−H) + γ(C−N)), 1376 (C=C, ph), 1416 (C−C, ph), 1460, 1255 (C−O), 1104, 1022 cm-1 (C−O−C), 869 (C−H, ph). The influence of the DOP content on the crosslinking, gel time, swelling, thermomechanical properties, and on the adhesive performances of the PHU thermosets was then evaluated and discussed below.

Fig. 1 FTIR spectra of PHU, modified PHU, TMPTC and DOP.

Curing kinetics by rheology


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As the addition of mono-functional amines, here dopamine (DOP), in thermosets formulation can adversely affect the formation of the network, the effect of the addition of DOP on the curing kinetics was systematically evaluated by rheology at 100 °C for 40 min (Fig. S1). The measurements were performed on the solvent-free PHU formulations with increasing content of DOP (0, 3.9, 7.7, 14.8 mol%) compared to TMPTC/HMDA (keeping an equimolar content of amine and cyclic carbonate groups for all formulations). All rheological data are summarized in Table S1. For all formulations, the loss modulus (G") was initially higher than the storage modulus (G'), confirming that PHU was not crosslinked before the measurement. Fig. S1 illustrates that G' increased faster than G" with the reaction time, and a crossover point was observed that corresponds to the gel point (G′ = G″ and/or tan δ = 1). As expected, the gelation time increased (from about 3 to 30 min, Fig.2), the storage moduli reduced (from 123.2 to 8.5 kPa, at 40 min, Table S1) and the crosslinking density reduced from 13.2 to 0.9 mol.m–3 with the content in dopamine (0 to 14.8 mol%, Fig.2). These results tend to confirm that part of the dopamine molecules react with the cyclocarbonate functions and are grafted on the resulting PHUs. However, at low dopamine content (10 mol% and below), this effect remains marginal and good PHUs thermosets are expected to be formed in these conditions. Nevertheless, more studies are required to elucidate the complex structure of this crosslinked system.


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Fig. 2 The crosslinking density (e) and gel time for the different PHU samples [PHU10 mol%, PHU43.9 mol%, PHU67.7 mol%, PHU814.8 mol% of DOP].

Swelling measurements The degree of crosslinking density of PHU thermosets after curing at 100 °C for 18 h was qualitatively studied by measuring the equilibrium water content (EWC-Eq.2) and gel content (GC-Eq.3) with the immersion of their freestanding films (0.125 cm3) in 10 mL of milli-Q water for 96 h at room temperature. The obtained values are reported in Table 1. EWC slightly increased from 38 ± 4 to 44 ± 5 % by raising the DOP molar ratio from 0 to 14.8 mol% (PHU1 to PHU8). The increase of the EWC may be attributed to the presence of polar functional groups (catechol) within the mussel-mimetic-crosslinked PHUs. The gel content was above 94% in all cases demonstrating the formation of highly cross-linked materials and the absence of free dopamine that could be extracted from the samples. This gel content was also high in THF confirming the absence of extractable short chains. Table 1. Formulation composition and characteristic properties of mussel-mimetic PHU thermosets

Sample code

TMPTC/HMDA(mol) a

b

GCc (%) CAd

EWC (%)

/DOP (mol%)

Water

THF

CCAe

Tgf (°C)

Tdg50%

Eh(MPa)

σui(MPa)

σfj (%)

PHU 1

1/1.5/0

38 ± 4

95.2

92.1

61 ± 2°

5B

35.3

331

12.7 ± 0.1

17.4 ± 0.1

5.8 ± 0.2

PHU 2

1/1.485/1.2

40 ± 3

94.1

93.8

61 ± 3°

5B

38.4

355

16.7 ± 0.2

23.8 ± 0.8

5.2 ± 0.4

PHU 3

1/1.475/2.0

41 ± 4

97.5

96.4

61 ± 3°

5B

39.3

360

19.6 ± 2.1

31.1 ± 0.3

5.3 ± 0.3

PHU 4

1/1.45/3.9

41 ± 6

98.2

96.7

59 ± 2°

5B

42.6

359

29.7 ± 2.6

34.2 ± 0.7

4.7 ± 0.3

PHU 5

1/1.425/5.8

42 ± 4

97.9

97.3

58 ± 3°

5B

42.8

361

21.1 ± 0.6

23.2 ± 1.5

3.1 ± 0.5

PHU 6

1/1.4/7.7

42 ± 7

96.4

98.0

58 ± 3°

5B

43.2

361

17.6 ± 0.7

20.1 ± 1.3

2.6 ± 0.1

PHU 7

1/1.375/9.5

43 ± 2

97.6

98.3

57 ± 4°

5B

43.3

360

16.5 ± 0.6

14.6 ± 0.6

1.3 ± 0.3

PHU 8

1/1.3/14.8

44 ± 5

98.2

99.1

57 ± 3°

5B

45.1

360

N.d

N.d

N.d


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a)

Optimum formulation compositions

b)

EWC: Equilibrium water content of self-standing films (0.125 cm3)

immersed in water for 96 h, at room temperature. Contact angle measurements, crosscuts),

f)

e)

Page 14 of 30

c)

GC: Gel content determined in water and THF

d)

CA:

CCA: Cross-cut adhesion test (5B-0% of coating area removed within

DSC-glass transition temperature, at heating rate 10 °C min−1,

degradation (Td50%), at heating rate 20 °C min−1,

h)

E: Young’s modulus,

i)

g)

TGA- temperatures at 50%

σu: Ultimate tensile strength and

j)

σf: Fracture stress

Thermal properties The thermal properties of crosslinked PHU with incorporated DOP (0 to 14.8 mol%) was evaluated by thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC) (Fig. S2). The temperature at 50% of degradation (Td50%) and glass transition temperature (Tg) values are reported in Table 1. All PHUs presented a high thermal stability with a Td50% that increased from 331 °C for PHU1 that did not contain any DOP, to 360 °C for PHU3 that contained only 2 mol% of DOP. At higher DOP content, the Td50% remained constant around 360 °C. The glass transition temperature (Tg) of PHU-thermosets was progressively increased with the DOP content from 35 °C (neat PHU1) to 45 °C (PHU8 containing 14.8 mol% of DOP). This Tg increase is assumed to be the result of the reduction of the chain mobility owing to presence of dihydroxybenzene functions that form strong H-bond interactions. Mechanical properties The structure-property relationships of mussel-mimetic PHU thermosets were investigated by conventional tensile tests. A variety of network structures was obtained by varying the TMPTC/HMDA/DOP molar ratios, while the processing conditions were maintained constant (see experimental section for details), Fig. S3. All data are also summarized in Table 1. The neat PHU0% DOP exhibited young’s modulus up to 12.7 MPa, ultimate tensile strength of 17.4 MPa


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and stress at break of 5.8 %. The presence of low DOP content (3.9 mol%, PHU4) had a remarkable beneficial impact on the young’s modulus with a 233% increase, i.e. from 12.7 for PHU1 to 29.7 MPa for PHU4, and on the ultimate tensile strength with a 196% increase, i.e. from 17.4 to 34.2 MPa. These improvements in the mechanical strength associated with ductile fracture and extensive plastic deformation of thermosets are likely attributed to the development of multiple hydrogen bonding interactions between modified PHUs and DOP, π-π interactions and eventually self-polymerized catechols. All the possible interactions in the modified PHU adhesives have been schematized in Figure 3. However, when higher DOP content (> 3.9 mol%) were introduced in the formulation, a decrease of the young’s modulus and stress at break were observed which demonstrates a transition from a ductile to a brittle fracture of adhesive materials with a lack of plastic deformation. The presence of a high amount of catechol probably restricts too much the mobility of the chains that leads to brittle fracture.


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Fig. 3 Overview of the possible interactions in bulk mussel-mimetic PHU adhesive-substrate interface.

Coating properties The solvent-free incorporated DOP containing PHUs were coated on a bare and cleaned aluminum with thickness of ~ 50 – 60 µm (see experimental section for details). Their adhesion strength was then evaluated by performing crosscut tests according to the ASTM D3359 standards. Whatever the coating, the edges of the cuts were completely smooth and none of the squares were removed from the coating. All tested coatings were thus all classified as 5B-0% removal of the coating, thus very adherent to the substrate, Table 1. The binding ability of the coatings was further evaluated in wet environment after immersing the coated substrate in water. The neat PHU coating was rapidly peeled off (Fig. 4a) from the substrate after 12h of immersion due to the high hydrophilicity of PHU1 (contact angle (CA) =


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61°, Table 1). In contrast, the coating containing DOP (PHU4) did not peel off when immersed in water for 48 h (Fig.4b), despite the coating being hydrophilic (Table 1). This comparative study reveals that the incorporation of DOP inside the PHU formulation is beneficial for improving the water resistance of the coating.

Fig. 4 Photographic images of bare Al-2024-T3 substrates coated with (a) neat PHU (peeling off in water after 12 h) and (b) Mussel-mimetic PHU thermoset (PHU4, 3.9 mol%-DOP, catechol-functionalized PHU) (no peeling off in water after 48 h).

Adhesion properties The influence of catechol on the adhesion performance of crosslinked PHUs was investigated by lap-shear tests (Fig. 5a) on aluminum substrates (Al-2024-T3) that is frequently used in aerospace and aircraft applications. The lap shear bonding strength (MPa and/or N.mm−2) was calculated by dividing the maximum load or force (N) by the adhesive surface area (mm2), using eq4. Fig. 5b shows that neat PHU (PHU1) was characterized by a shear adhesion strength of 9.1 ± 3.1 MPa. The shear strength was strongly improved by the addition of DOP, with a maximum value of 24.1 ± 1.7 MPa with only 3.9 mol% DOP (PHU4), which represents a 264% increase compared to neat PHU1 (Fig. 5b). Moreover, the adhered metal lap joints failed in a cohesive manner for all samples, with both surfaces that remained covered by the adhesive (Table S2).


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The improvement of the adhesive properties was therefore attributed to the improvement of the cohesive strength of the glue via covalent and non-covalent interactions as illustrated in Figure 3. These observations are in full agreement with the mechanical properties (Table 1, Figure S3). However, when the DOP content was further increased in the formulation, the adhesion performances progressively decreased with an adhesion strength of 13.1 ± 3.4 MPa for PHU7 (9.5 mol% DOP) and 3.6 ± 2.1 MPa for PHU8 (14.8 mol% DOP). This decrease might be explained by the slowing down of the curing kinetics at high DOP content as demonstrated by rheological measurements (Fig. 2), and by the transition from a ductile to a brittle material as evidenced by mechanical measurements (Fig. S4).


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Fig. 5 Evolution of lap shear strength of adhesively bonded joints of neat and mussel-mimetic polyhydroxyurethanes was investigated by using instron-5594 apparatus, (a) Force vs displacement curves of neat (PHU1, 0% DOP) and group of mussel-mimetic PHU thermosets (PHU2-8, 0-14.8 mol% DOP) evaluated for affixed aluminum substrates (b) Influence of quantity of dopamine on shear adhesion strength of PHU adhesives on aluminum substrates, (c) Force vs displacement curves of PHU4 (3.9 mol%-DOP) evaluated for


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similar attachment of substrates (Aluminum, Stainless steel, Wood (W), Plexiglass (Gl) and Polyethylene (PE), (d) The shear adhesion strength of PHU4 as a function of adherently bonded similar substrates, (e) Force vs displacement curves for (PHU4, 3.9 mol% DOP) for dissimilar attachment of substrates and (f) the shear adhesion strength of PHU4 on dissimilar substrates.

The development of an adhesive formulation that is able to efficiently glue a large diversity of substrates is challenging due to their diverse chemical nature, surface energy, wettability and roughness. In this study, the highest performing mussel-inspired glue for aluminum (PHU4, 24.1 MPa, Al-Al) was then tested for gluing similar/dissimilar substrates such as stainless steel (SS), wood (W), plexiglass (Gl) and polyethylene (PE) (Fig. 5c-f). Interestingly, the highest shear adhesion strength of 28.2 MPa was measured for wood (W–W). It remained high for SS with a value of 22.1 MPa, and slightly decreased to 17.9 MPa for Gl. Although lower, the shear adhesion strength for PE remained satisfactory with a value of 4.76 MPa (Fig. 5c-d, Table S3). This lower value for PE is the result of the low surface roughness and hydrophobic character of the substrate that do not favour the interaction between catecholhydroxyurethane groups and the substrate. In most cases, we noticed a mixture of failure modes (cohesive-C.F.-/adhesive-A.F.- failure modes) in adhered joints. For PE, an adhesive failure is always noted, indicating a low interaction between the hydrophilic glue and the hydrophobic substrate, although the adhesive performances are more than satisfactory. Interestingly, the adhesive strength on PE obtained with the DOP-modified PHU (PHU4, 4.76 MPa) is much higher than the one of unmodified PHU (PHU1, 1.18 MPa), demonstrating that the presence of dopamine improves the interaction between the adhesive and the substrate. The failure pattern of adhesively bonded joints is summarized in Table S3 and schematically presented in Fig. S4.


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The highest performing formulation (PHU4) was also tested for affixing dissimilar substrates (Al-W, Al-SS, Al-PE, Al-Gl, SS-PE…etc, Fig. 5e-f, Table S3). PHU4 is highly efficient to glue wood to metals (either to Al and SS) with a remarkable adhesion strength of 25 MPa for Al-W and of 23.8 MPa for SS-W. High adhesive performances are also noted for Al-SS (21.1 MPa). Although slightly lower, the lap shear strengths remained high when PHU4 was used to assemble plexiglass to wood (18.2 MPa), to Al (18.2 MPa) or to SS (16.3 MPa). Importantly, this glue is also efficient to glue the hydrophobic plastic (PE) to the different substrates with lap shear strengths of 13.3 MPa for Al, 10.9 MPa for SS, 8.3 MPa for W and 6.7 MPa for Gl. Benchmarking Finally, the high shear bonding strength of catechol-bearing-PHU thermoset adhesive (PHU4) was benchmarked against commercial (Teromix-6700 and Araldite®2000), petrochemicallybased (PHU(M-1),35 PHU-5C)32 and bio-based (PHU-H3)33 polyurethane adhesives (Fig. 6). The processing conditions were held constant for fair comparison. The results are shown in Fig. 6. When cured at 25 °C, the commercial PU adhesives present the best adhesion performance with lap shear strength values up to 21.7 MPa for Araldite®2000 and up to 12.5 MPa for Teromix6700, whereas PHU adhesives are characterized by a low shear strength (PHU(M-1),35 PHU5C,32 PHU-H333 and PHU4: 1.9, 3.3, 2.2 and 3.6 MPa, respectively). The low adhesive performances of PHUs is the result of the slow aminolysis of the cyclic carbonates at room temperature (and thus uncomplete curing), compared to the fast isocyanate/alcohol reaction observed for the conventional PUs. As expected, the adhesive performances of all PHU are strongly improved when cured at 100 °C for 18 h. At this temperature, the amine/cyclic carbonate reaction (and therefore the curing) is promoted. Impressively, the mussel-mimetic PHU adhesive (PHU4) competes the performance of universal commercial-PUs when cured


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under these conditions with a remarkable lap shear strength of 24.1 MPa. These performances surpass those of the state-of-the art PHUs,32,33,35 even those that have been reinforced by ZnO nanofillers for optimal adhesion to aluminum (PHU 5C). This benchmarking study clearly highlights that well-designed PHU adhesives are realistic alternatives to commercial PU adhesives, provided that hot curing is permitted.

Fig. 6 High performant mussel-mimetic PHU thermoset adhesive (PHU4) benchmarked against commercial PU (Teromix-6700 and Araldite®2000+) and reported PHU adhesives (thus, TMPTC/EDR-148, PHU5C: TMPTC/HMDA/PDMS/CC-ZnO), and PHU-H3: CSBO/HMDA/CC-ZnO) evaluated for aluminum substrate. The curing conditions (time and temperature), amount of adhesive, overlapping/gluing area were held constant.

CONCLUSIONS Novel mussel-mimetic polyhydroxyurethane (PHU) thermoset adhesives were prepared by the solvent-free polyaddition of a tricyclic carbonate (TMPTC), a diamine (HMDA) and dopamine (DOP). We have systematically studied the influence of DOP content on the formulation performances such as the crosslinking, thermomechanical and adhesion properties. We found


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that the incorporation of only 3.9 mol% DOP to the PHU formulation strongly increased the young’s modulus by 233%, and the ultimate tensile strength by 196%, providing a PHU with unprecedented adhesion performances. Indeed, an impressive adhesion strength of 28.2 MPa was noted for wood, and remarkable shear adhesion strengths were measured for metal substrates with values as high as 24.1 MPa for aluminum, 22.1 MPa for stainless steel, but also for organic glass such as plexiglass (17.9 MPa). Importantly, this formulation was also able to efficiently glue substrates of different nature, such as a hydrophobic plastic (polyethylene) with metals (SS or Al), wood or plexiglass. The adhesion performances of our product surpass those of PHU that do not contain the catechol groups. A benchmarking study has demonstrated that the catecholbearing PHU glues are competing with the adhesion performances of commercial PU glues (Teromix-6700 and Araldite®2000 plus), at least when a thermal curing is implemented to overcome the low reactivity of cyclic carbonate with amines. We have demonstrated that the catechol groups improved both the cohesion of the glue network and its adhesion to the substrate. The valorization of CO2, the solvent-free process without any release of toxic reagent, and the use of dopamine (that can be produced from tyrosine70–72 or phenylalanine73 amino acids) benefit the environment and align with principles of Green Chemistry.74,75 Current efforts are now dealing with the optimization of the formulations to enable curing at room temperature, and with the use of all bio-sourced products. ASSOCIATED CONTENT Supporting Information The supporting information is available Rheology measurements (Fig.S1 and Table S1), thermal (Fig.S2) and mechanical (Fig.S3) properties, lap shear strength and failure mode of adhesive joints (Table S2-S3 and Fig.S4).


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AUTHOR INFORMATION Corresponding Author E-mail: [email protected]; Tel: +3243663465 Present Addresses Center for Education and Research on Macromolecules (CERM), CESAM Research Unit, University of Liège, allée du 6 août, Building B6A, Agora Square, 4000 Liège, Belgium Author Contributions. S.P. carried out all experiments. JM.T. advised S.P. in rheology and thermo-mechanical measurements, and contributed to the discussion of these results. B.G. advised and supervised S.P. in the formulations to be used and in the synthesis of the cyclic carbonate by the CO2 chemistry. C. J. and C.D. are the supervisor and co-supervisor, respectively, of the PhD thesis of S.P., and are at the origin of the project. C.D. suggested to use dopamine in the formulation to improve the performances of the coatings. Funding Sources. Region Wallonne in the Frame of the Flycoat project. Belgian Science Policy (BELSPO)

in the frame of the "Interuniversity Attraction Poles

Programme (IAP VII/5) – Functional Supramolecular Systems". Fonds de la Recherche Scientifique (FRS-FNRS) NOTES The authors declare no competing financial interest ACKNOWLEDGMENT


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The authors of Liège thank the “Region Wallonne” in the frame of the Flycoat project, the "Belgian Science Policy" in the frame of the "Interuniversity Attraction Poles Programme (IAP VII/5) – Functional Supramolecular Systems" and the "Fonds National pour la Recherche Scientifique” (F.R.S.-FNRS) for financial supports. C.D. is Research Director by F.R.S.-FNRS. REFERENCES (1)

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TABLE OF CONTENT

SYNOPSIS The incorporation of catechols to CO2-sourced poly(hydroxyurethane) provides highperformance thermoset adhesives for a broad range of substrates (plastics, metals, glass, wood, etc).


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Catechol Containing Polyhydroxyurethanes as High Performance

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